JPH07500532A - 平衡流動クラッキング触媒からの流動クラッキング触媒の製造方法 - Google Patents
平衡流動クラッキング触媒からの流動クラッキング触媒の製造方法Info
- Publication number
- JPH07500532A JPH07500532A JP5508409A JP50840993A JPH07500532A JP H07500532 A JPH07500532 A JP H07500532A JP 5508409 A JP5508409 A JP 5508409A JP 50840993 A JP50840993 A JP 50840993A JP H07500532 A JPH07500532 A JP H07500532A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- zeolite
- equilibrium
- fcc
- catalysts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims description 153
- 238000005336 cracking Methods 0.000 title description 20
- 238000004519 manufacturing process Methods 0.000 title description 9
- 239000010457 zeolite Substances 0.000 claims description 65
- 229910021536 Zeolite Inorganic materials 0.000 claims description 62
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910001868 water Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 230000000704 physical effect Effects 0.000 claims description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 6
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000000463 material Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000011282 treatment Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000000571 coke Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- -1 aluminum ions Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 229910052770 Uranium Inorganic materials 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- 101100045694 Caenorhabditis elegans art-1 gene Proteins 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011888 autopsy Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010001 crabbing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/21—Faujasite, e.g. X, Y, CZS-3, ECR-4, Z-14HS, VHP-R
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/786,663 US5182243A (en) | 1991-11-01 | 1991-11-01 | Process for preparing fluidized cracking catalysts from equilibrium fluidized cracking catalysts |
| US786,663 | 1991-11-01 | ||
| PCT/US1992/008312 WO1993008911A1 (fr) | 1991-11-01 | 1992-09-30 | Procede de preparation de catalyseurs de craquage fluidises a partir de catalyseurs de craquage fluidises d'equilibre |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07500532A true JPH07500532A (ja) | 1995-01-19 |
Family
ID=25139252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5508409A Pending JPH07500532A (ja) | 1991-11-01 | 1992-09-30 | 平衡流動クラッキング触媒からの流動クラッキング触媒の製造方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5182243A (fr) |
| EP (1) | EP0610293A4 (fr) |
| JP (1) | JPH07500532A (fr) |
| AU (1) | AU2780792A (fr) |
| CA (1) | CA2119231A1 (fr) |
| MX (1) | MX9206287A (fr) |
| WO (1) | WO1993008911A1 (fr) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1078100C (zh) * | 1998-08-14 | 2002-01-23 | 中国石油化工集团公司 | 含y型沸石的失活催化剂的再处理方法 |
| US6942784B2 (en) * | 2000-09-22 | 2005-09-13 | Engelhard Corporation | Structurally enhanced cracking catalysts |
| CN101757944B (zh) * | 2008-12-25 | 2012-05-30 | 中国石油化工股份有限公司 | 一种增产液化气的裂化助剂及其制备方法 |
| CN102125872B (zh) * | 2011-01-17 | 2013-05-29 | 湖南聚力催化剂股份有限公司 | 用FCC废催化剂合成含NaY沸石多孔微球材料的方法 |
| US8216532B1 (en) * | 2011-06-17 | 2012-07-10 | Vierheilig Albert A | Methods of recovering rare earth elements |
| US10286391B2 (en) | 2012-02-17 | 2019-05-14 | Inaeris Technologies, Llc | Catalyst system having meso and macro hierarchical pore structure |
| CN106140296A (zh) * | 2015-04-22 | 2016-11-23 | 中国石油化工股份有限公司 | 一种催化裂化废催化剂再利用的方法 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3777006A (en) * | 1972-01-21 | 1973-12-04 | Grace W R & Co | Process for preparing zeolitic bodies having high strength characteristics |
| US4309313A (en) * | 1980-05-23 | 1982-01-05 | W. R. Grace & Co. | Synthesis of cesium-containing zeolite, CSZ-1 |
| US4482530A (en) * | 1982-12-29 | 1984-11-13 | Ethyl Corporation | Method of making zeolite Y |
| US4550090A (en) * | 1983-08-26 | 1985-10-29 | Mobil Oil Corporation | Regeneration of ZSM-5 type catalyst with a source of alkali or alkaline earth metal cations or ammonia |
| US4699893A (en) * | 1985-04-29 | 1987-10-13 | Engelhard Corporation | Fluid cracking catalyst and method of making same from waste catalyst manufacture fines |
| US4631262A (en) * | 1985-06-05 | 1986-12-23 | Engelhard Corporation | Method of making seed solution useful in zeolite catalyst manufacture |
| US4826792A (en) * | 1985-11-21 | 1989-05-02 | Mobil Oil Corporation | Method of noble metal-zeolite catalyst activation with Bronsted acid compound |
| US5001094A (en) * | 1987-06-22 | 1991-03-19 | Mobil Oil Corporation | Hydrocarbon conversion process including acidic zeolite reactivation |
| US4784980A (en) * | 1987-07-15 | 1988-11-15 | Amoco Corporation | Process for preparing zeolite A from spent cracking catalyst |
| CA2000327A1 (fr) * | 1988-11-16 | 1990-05-16 | Lawrence B. Dight | Catalyseurs fcc a teneur ultra-elevee en zeolite; methode pour les preparer a partir de microspheres conestituees d'un melange d'argiles de kaolin calcinees |
| US5143878A (en) * | 1990-06-04 | 1992-09-01 | Texaco Inc. | Zeolite treating process |
-
1991
- 1991-11-01 US US07/786,663 patent/US5182243A/en not_active Expired - Lifetime
-
1992
- 1992-09-30 AU AU27807/92A patent/AU2780792A/en not_active Abandoned
- 1992-09-30 WO PCT/US1992/008312 patent/WO1993008911A1/fr not_active Application Discontinuation
- 1992-09-30 JP JP5508409A patent/JPH07500532A/ja active Pending
- 1992-09-30 EP EP92921955A patent/EP0610293A4/fr not_active Withdrawn
- 1992-09-30 CA CA002119231A patent/CA2119231A1/fr not_active Abandoned
- 1992-10-30 MX MX9206287A patent/MX9206287A/es not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CA2119231A1 (fr) | 1993-05-13 |
| US5182243A (en) | 1993-01-26 |
| EP0610293A4 (fr) | 1995-02-01 |
| EP0610293A1 (fr) | 1994-08-17 |
| WO1993008911A1 (fr) | 1993-05-13 |
| AU2780792A (en) | 1993-06-07 |
| MX9206287A (es) | 1993-05-01 |
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